CN110449183A - Ionic iron (III) complex is preparing the application in allylic amines compound - Google Patents
Ionic iron (III) complex is preparing the application in allylic amines compound Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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Abstract
The invention discloses ionic iron (III) complexs to prepare the application in allylic amines compound, i.e., with molecular formula for [(RNCH2CH2NR)CH][FeBr4] (R is tert-butyl) contain 1, ionic iron (III) complex of 3- di-t-butyl Imidazole cation is catalyst, using di-t-butyl peroxide as oxidant, by the oxidative coupling reaction of aminated compounds and allyl hydrocarbon compound come synthesis of allyl aminated compounds.The present invention is applied widely, it is applied not only to the aromatic amine containing electron-withdrawing group, and it is also effective for the aromatic amine containing electron-donating group, this is the first case that allylic amines compound is prepared by the oxidative coupling reaction through aminated compounds and allyl hydrocarbon compound of Fe-series catalyst realization.
Description
The present invention is a kind of entitled method for preparing allylic amines compound, the applying date is December 8 in 2017
Day, application No. is the divisional applications of 201711298546X patent application, belong to application technology part.
Technical field
The invention belongs to the preparation technical fields of organic compound, and in particular to the preparation side of allylic amines compound
Method.
Background technique
Allylic amines compound is widely present in natural products, pesticide, polymer as a kind of skeleton structure of key
In drug molecule.The substrate using preparatory functionalization is needed when this kind of compound of conventional synthesis, such as halogenated hydrocarbons passes through Bu Hewa
Er De-Hartwig (Buchwald-Hartwig) cross-coupling reaction come synthesize (referring to J. F. Hartwig,Acc. Chem. Res., 2008,41,1534).Such method needs, which give off, the halide seriously polluted to environment, and step
More, Atom economy is poor.Therefore developing more environmentally friendly, efficient synthetic method has very strong practical application value.
In recent years, being reacted by the direct aminatin of carbon-hydrogen link becomes the one of synthesizing aminated compounds to construct carbon-nitrogen bond
A new method, this method avoid the uses of halogenated hydrocarbons, have better Atom economy and environment friendly, and the prior art is adopted
Catalyst hasβDi-imidogen copper (I) complex, tetrabutylammonium iodide, but these methods all have certain limitation
Property, the mainly narrow scope of application of substrate, are only applicable to the aromatic amine containing electron-withdrawing group, and for containing supplied for electronic
The aromatic amine of group can not carry out under existence conditions.
In past 10 years, Fe-series catalyst is because having many advantages, such as cheap and easy to get, less toxic or nontoxic, good biocompatibility
And be developed rapidly, but up to the present, it yet there are no Fe-series catalyst in aromatic amine and allyl hydrocarbon compound
Application report in oxidative coupling reaction carrys out synthesis of allyl aminated compounds.Therefore, efficient Fe-series catalyst is developed, is passed through
The oxidative coupling reaction of aromatic amine and allyl hydrocarbon compound is come to construct allylic amines compound be to meet Green Chemistry
Demand for development, be that there is greatly innovative and application value.
Summary of the invention
The object of the present invention is to provide a kind of new methods of synthesis of allyl aminated compounds, i.e., are with molecular formula
[(tBuNCH2CH2NtBu)CH][FeBr4] ionic iron (III) complex of the Imidazole cation of di-t-butyl containing 1,3- be
Catalyst, using di-t-butyl peroxide as oxidant, pass through the oxidative coupling reaction of aromatic amine and allyl hydrocarbon compound
Carry out synthesis of allyl aminated compounds.[(tBuNCH2CH2NtBu)CH][FeBr4] it is a kind of simple and easy to get and in air
Stable iron (III) complex with clear structure.
To achieve the above object of the invention, the technical solution adopted by the present invention is that:
A method of allylic amines compound is prepared, is included the following steps, mixed catalyst, arylamine, oxidant, allyl
Hydrocarbon compound and solvent, reaction obtain allylic amines compound；The chemical structural formula of the catalyst is as follows:
。
In above-mentioned technical proposal, the solvent is ethyl acetate；The oxidant is di-t-butyl peroxide；The arylamine
For primary aromatic amine and aromatic amine；The allyl hydrocarbon compound is cyclohexene.
In above-mentioned technical proposal, the temperature of the reaction is 110~140 DEG C, and the time is 18~30 hours.
It in above-mentioned technical proposal, after reaction, is cooled to room temperature, reaction product is extracted with ethyl acetate, and passes through column layer
Analysis carries out quantitative analysis.
In above-mentioned technical proposal, with the meter of substance, di-t-butyl peroxide is 1~1.6 times of the dosage of arylamine, catalysis
Agent dosage is 3~6 % of the dosage of arylamine.
In preferred technical solution, with the meter of substance, di-t-butyl peroxide is 1.5 times of the dosage of arylamine, catalysis
Agent dosage is 5 mol% of the dosage of arylamine；Temperature is 130 DEG C, is reacted 24 hours.
Invention additionally discloses ionic iron (III) complexs to prepare the application in allylic amines compound；It is described from
The chemical structural formula of subtype iron (III) complex is as follows:
。
In the application, using arylamine, allyl hydrocarbon compound as raw material when preparing allylic amines compound.
Invention additionally discloses ionic iron (III) complex answering in catalysis arylamine, the reaction of allyl hydrocarbon compound
With；The chemical structural formula of ionic iron (III) complex is as follows:
。
The invention also discloses a kind of ionic iron (III) complexs of Imidazole cation Han 1,3- di-t-butyl, can
It is expressed by the following chemical structure formula:
。
The preparation method of above-mentioned ionic iron (III) complex for containing 1,3- di-t-butyl Imidazole cation, including with
1,3- di-t-butyl imidazoline villaumite and NaBr are successively added in the tetrahydrofuran solution of ferric bromide by lower step, reaction
Vacuum pumps solvent afterwards, and hexane washing is drained, extracted with tetrahydrofuran, and centrifugal clear liquid transfer is added hexane in clear liquid and ties again
Red-brown crystals are precipitated in crystalline substance at room temperature, for ionic iron (III) complex of the di-t-butyl Imidazole cation containing 1,3-.
Above-mentioned reaction process can indicate as follows:
Since above-mentioned technical proposal is used, compared with the prior art, the present invention has the following advantages:
1, the present invention passes through aromatic amine compound and allylic hydrocarbons for the first time using iron (III) complex as single-component catalyst
The oxidative coupling reaction of class compound has synthesized allylic amines compound, and catalyst structure is clear, component is single, synthetic method
Simply, air-stable is easy to operate, while having the characteristics that inexpensive, green, environmental-friendly, is conducive to large-scale commercial synthesis and answers
With.
2, preparation method disclosed by the invention is applied widely, is applied not only to the aromatic amine containing electron-withdrawing group, and
It is also effective for the aromatic amine containing electron-donating group, the scope of application of aromatic amine compound has been widened significantly.It compares
Compared with previous existing literature procedure only can be suitably used for the aromatic amine compound containing electron-withdrawing group, for containing confession
The aromatic amine compound of electron group can not carry out.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment one: the Imidazole cation of di-t-butyl containing 1,3- (molecular formula be [(tBuNCH2CH2NtBu)CH][FeBr4])
The synthesis of ionic iron complex
Successively by 1,3- di-t-butyl imidazoline villaumite (0.22 gram, 1.0 mMs) and NaBr(0.15 grams, 1.5 mMs) plus
Enter into the tetrahydrofuran solution of ferric bromide (0.29 gram, 1.0 mMs), is reacted 24 hours under 60 °C, vacuum pumps molten
Agent, hexane washing, drains, is extracted with tetrahydrofuran, and hexane recrystallization is added in clear liquid, analyses at room temperature for centrifugal clear liquid transfer
Red-brown crystals out, yield 90%.
Elemental analysis is carried out to product, as a result as follows:
Elemental analysis
This complex [(tBuNCH2CH2NtBu)CH][FeBr4] be in the form of ion pair existing for, wherein [FeBr4]-Pass through
Raman spectrum is characterized, and finds it in 204 cm-1There is characteristic peak at place.
Complex cationic portion [(tBuNCH2CH2NtBu)CH]+Characterized by mass spectrum, find its
There is a molecular ion peak at 183.1861, theoretically this molecular ion peak is surveyed consistent with theory 183.1861.
Prove that gained compound is target compound, chemical structural formula is as follows:
。
Embodiment two: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis aniline and cyclohexene oxidative coupling reaction
It is sequentially added in reaction flask aniline (46 microlitres, 0.5 mM), catalyst (14 milligrams, 0.025 mM), peroxide
Change di-t-butyl (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) reacts at 130 DEG C
It 24 hours, is cooled to room temperature after reaction, product column Chromatographic purification, (is 1: 50 with ethyl acetate/petroleum ether volume ratio
Mixed solvent is solvent), yield 95%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.10-7.06 (m, 2H), 6.61-6.57 (m, 1H), 6.54-
6.51 (m, 2H), 5.77-5.74 (m, 1H), 5.68-5.65 (m, 1H), 3.90 (s, 1H), 3.51 (s,
1H), 1.95-1.93 (m, 2H), 1.84-1.79 (m, 1H), 1.67-1.52 (m, 3H)。
Embodiment three: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis open-chain crown ether and cyclohexene oxidative coupling
Reaction
It is sequentially added in reaction flask open-chain crown ether (54 milligrams, 0.5 mM), and catalyst (14 milligrams, 0.025 mmoles
You), di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is 120
It reacts 28 hours at DEG C, is cooled to room temperature after reaction, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio
Mixed solvent for 1: 20 is solvent), yield 83%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 6.89 (d, J = 8.1 Hz, 2H), 6.46 (d, J = 8.4
Hz, 2H), 5.76-5.72 (m, 1H), 5.69-5.64 (m, 1H), 3.87 (s, 1H), 3.26 (s, 1H),
2.15 (s, 3H), 1.94-1.92 (m, 2H), 1.81-1.78 (m, 1H), 1.66-1.50 (m, 3H)。
Example IV: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis p-tert-butyl-aniline and cyclohexene oxidation it is even
Connection reaction
It is sequentially added in reaction flask p-tert-butyl-aniline (80 microlitres, 0.5 mM), and catalyst (14 milligrams, 0.025 mmoles
You), di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is 110
It reacts 30 hours at DEG C, is cooled to room temperature after reaction, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio
Mixed solvent for 1: 50 is solvent), yield 93%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.11-7.09 (m, 2H), 6.49-6.47 (m, 2H), 5.76-
5.71(m, 1H), 5.68-5.64 (m, 1H), 3.87 (s, 1H), 3.29 (s, 1H), 1.95-1.91 (m,
2H), 1.82-1.76 (m, 1H), 1.62-1.52 (m, 3H), 1.19 (s, 9H)。
Embodiment five: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis parachloroanilinum and cyclohexene oxidative coupling it is anti-
It answers
It is sequentially added in reaction flask parachloroanilinum (64 milligrams, 0.5 mM), catalyst (14 milligrams, 0.025 mM),
Di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is at 120 DEG C
Reaction 28 hours, is cooled to room temperature, product column Chromatographic purification after reaction, (with ethyl acetate/petroleum ether volume ratio for 1:
100 mixed solvent is solvent), yield 96%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.12-7.08 (m, 2H), 6.55-6.51 (m, 2H), 5.88-
5.83 (m, 1H), 5.74-5.69 (m, 1H), 3.93 (s, 1H), 3.60 (s, 1H), 2.04-2.02 (m,
2H), 1.92-1.85(m, 1H), 1.75-1.55 (m, 3H).
Embodiment six: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis para-bromoaniline and cyclohexene oxidative coupling reaction
It is sequentially added in reaction flask para-bromoaniline (86 milligrams, 0.5 mM), catalyst (14 milligrams, 0.025 mM),
Di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is at 140 DEG C
Reaction 18 hours, is cooled to room temperature, product column Chromatographic purification after reaction, (with ethyl acetate/petroleum ether volume ratio for 1:
50 mixed solvent is solvent), yield 93%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.23-7.20 (m, 2H), 6.49-6.45 (m, 2H), 5.87-
5.82 (m, 1H), 5.72-5.68 (m, 1H), 3.91 (s, 1H), 3.60 (s, 1H), 2.05-1.99 (m,
2H), 1.90-1.84 (m, 1H), 1.74-1.54 (m, 3H)。
Embodiment seven: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis the oxidative coupling to cyano-aniline and cyclohexene
Reaction
It is sequentially added in reaction flask to cyano-aniline (59 milligrams, 0.5 mM), and catalyst (14 milligrams, 0.025 mmoles
You), di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is 110
It reacts 30 hours at DEG C, is cooled to room temperature after reaction, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio
Mixed solvent for 1: 50 is solvent), yield 95%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.30 (d, J = 8.8 Hz, 2H), 6.48 (d, J = 8.8
Hz, 2H), 5.84-5.79 (m, 1H), 5.62-5.59 (m, 1H), 4.29 (s, 1H), 3.92 (s, 1H),
1.96-1.95 (m, 2H), 1.85-1.79 (m, 1H), 1.68-1.51 (m, 3H)。
Embodiment eight: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis paranitroanilinum and cyclohexene oxidative coupling
Reaction
It is sequentially added in reaction flask paranitroanilinum (69 milligrams, 0.5 mM), and catalyst (14 milligrams, 0.025 mmoles
You), di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is 130
It reacts 24 hours at DEG C, is cooled to room temperature after reaction, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio
Mixed solvent for 1: 50 is solvent), yield 98%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.06 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 8.0
Hz, 2H), 5.95-5.91 (m, 1H), 5.71-5.68 (m, 1H), 4.67-4.65 (m, 1H), 4.08-4.07
(m, 1H), 2.06-2.05 (m, 2H), 1.97-1.91 (m, 1H), 1.77-1.65(m, 3H)。
Embodiment nine: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis the oxidative coupling to antifebrin and cyclohexene
Reaction
It is sequentially added in reaction flask to antifebrin (68 milligrams, 0.5 mM), and catalyst (14 milligrams, 0.025 mmoles
You), di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is 120
It reacts 28 hours at DEG C, is cooled to room temperature after reaction, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio
Mixed solvent for 1: 10 is solvent), yield 92%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3):7.82-7.79 (m, 2H), 6.58-6.55 (m, 2H), 5.91-5.86
(m, 1H), 5.72-5.68 (m, 1H), 4.41 (s, 1H), 4.05 (s, 1H), 2.48 (s, 3H), 2.04-
2.02 (m, 2H), 1.94-1.88 (m, 1H), 1.75-1.61 (m, 3H)。
Embodiment ten: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis aniline and cyclopentene oxidative coupling reaction
It is sequentially added in reaction flask aniline (46 microlitres, 0.5 mM), catalyst (14 milligrams, 0.025 mM), peroxide
Change di-t-butyl (138 microlitres, 0.75 mM), cyclopentene (2 milliliters), ethyl acetate (0.5 milliliter) reacts at 140 DEG C
It 18 hours, is cooled to room temperature after reaction, product column Chromatographic purification, (is 1: 50 with ethyl acetate/petroleum ether volume ratio
Mixed solvent is solvent), yield 85%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3):7.11-7.07 (m, 2H), 6.63-6.59 (m, 1H), 6.55-6.53
(m, 2H), 5.89-5.87 (m, 1H), 5.76-5.74 (m, 1H), 4.48-4.45 (m, 1H), 2.45-2.35
(m, 1H), 2.29-2.20 (m, 2H), 1.61-1.54 (m, 1H)。
Embodiment 11: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis methylphenylamine and cyclohexene oxidation it is even
Connection reaction
It is sequentially added in reaction flask methylphenylamine (54 microlitres, 0.5 mM), and catalyst (14 milligrams, 0.025 mmoles
You), di-t-butyl peroxide (138 microlitres, 0.75 mM), cyclohexene (2 milliliters), ethyl acetate (0.5 milliliter) is 130
It reacts 24 hours at DEG C, is cooled to room temperature after reaction, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio
Mixed solvent for 1: 100 is solvent), yield 91%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3):7.24-7.20 (m, 2H), 6.78 (d, J = 8.0 Hz, 2H),
6.70-6.66 (m, 1H), 5.92-5.88 (m, 1H), 5.62 (d, J = 8.0 Hz, 1H), 4.46-4.42 (m,
1H), 2.77 (s, 3H), 2.04-2.02 (m, 2H), 1.85-1.78 (m, 2H), 1.66-1.56 (m, 3H)。
Claims (6)
1. ionic iron (III) complex is preparing the application in allylic amines compound；Ionic iron (III) cooperation
The chemical structural formula of object is as follows:
。
2. application according to claim 1, which is characterized in that with arylamine, allyl when preparing allylic amines compound
Hydrocarbon compound is raw material.
3. application according to claim 2, which is characterized in that prepare allylic amines compound and include the following steps, mix
Catalyst, arylamine, oxidant, allyl hydrocarbon compound and solvent are closed, reaction obtains allylic amines compound；It is described molten
Agent is ethyl acetate；The oxidant is di-t-butyl peroxide；The arylamine is primary aromatic amine and aromatic amine；It is described
Allyl hydrocarbon compound is cyclohexene.
4. application according to claim 2, which is characterized in that the temperature of the reaction is 110~140 DEG C, the time 18
~30 hours.
5. application according to claim 2, which is characterized in that after reaction, be cooled to room temperature, reaction product acetic acid
Ethyl ester extraction, is chromatographed by column and carries out quantitative analysis.
6. application according to claim 2, which is characterized in that with the meter of substance, di-t-butyl peroxide is arylamine
1~1.6 times of dosage, catalyst amount are 3~6 % of the dosage of arylamine.
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| WO2020087233A1 (en) * | 2018-10-29 | 2020-05-07 | 南通纺织丝绸产业技术研究院 | Application of ionic iron (iii) complex as catalyst in preparation of benzylamine compound |
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| CN107935860B (en) | 2019-09-10 |
| CN107935860A (en) | 2018-04-20 |
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